Activities in Liquid Fe-V-O and Fe-B-O Alloys

R . J . FRUEHAN
The a c t i v i t i e s in liquid F e - V - O and F e - B - O alloys have b e e n d e t e r m i n e d u s i n g the following
galvanic c e l l s
Cr-Cr2Os(s) f ZrO2(CaO) I F e - V - O

(l,

s a t u r a t e d with oxide)

Cr-Cr2Os(s) ] ThO2(Y2Os) t F e - V - O (l, s a t u r a t e d with oxide)

Cr-Cr2Os(s) j ZrO~(CaO) I F e - B - O (/, B~O3 s a t u r a t e d with Alg)s)
The s o l u b i l i t y of oxygen in F e - V a l l o y s at 1600~ d e c r e a s e s with i n c r e a s i n g v a n a d i u m content
to a m i n i m u m of about 180 ppm at 3 wt pct V, and then i n c r e a s e s to over 4000 ppm at 36.3 wt
pct V. Vanadium was found to d e c r e a s e the activity coefficient of oxygen and the value of the
i n t e r a c t i o n coefficient e o(V) at infinite dilution of v a n a d i u m is - 0 . 1 4 . The activity of v a n a d i u m
was c a l c u l a t e d f r o m the m e a s u r e d e l e c t r o m o t i v e force, and log VV was found to be r e p r e s e n t e d
well by the q u a d r a t i c f o r m a l i s m for N v < 0.4:
2
log ~V = - 0 . 7 0 N F e - 0.30
At 1550~ b o r o n d e c r e a s e s the s o l u b i l i t y of oxygen down to about 80 ppm at 0.67 wt pct B in
F e - B m e l t s in e q u i l i b r i u m with B203 s a t u r a t e d with A12Os (NAlzO3 = 0.087). The b o r o n deoxidation product, K ' = (wt pct B)2(wt pct 0) 3 at infinite dilution of b o r o n is 4.4 10 -9 and 1.5 10 -9
at 1550 ~ and 1600~ r e s p e c t i v e l y . B o r o n d e c r e a s e s the a c t i v i t y coefficient of oxygen in liquid
i r o n , and the value of the i n t e r a c t i o n coefficient e~B) is - 2 . 6 at infinite dilution of boron. The
activity coefficient of boron at infinite dilution (TB) is 0.083 at 1550~

THE

c h e m i c a l b e h a v i o r of oxygen in F e - V a l l o y s has
b e e n the s u b j e c t of n u m e r o u s i n v e s t i g a t i o n s . However,
t h e s e i n v e s t i g a t o r s have r e p o r t e d a s i g n i f i c a n t l y wide
r a n g e of v a l u e s for the i n t e r a c t i o n coefficient e o(V)
e (V)
d(log fo)
o = d(wt %V)

[1]

D a s t u r and Chipman, 1 Schenck and S t e i n m e t z , 2 and P a r g e t e r 3 e q u i l i b r a t e d F e - V a l l o y s c o n t a i n i n g up to 1.3 pct

V with h y d r o g e n - w a t e r vapor m i x t u r e s at 1600~ and

r e l a t i v e to solid boron.

v a r i e d f r o m 1 10 -9 to 2.6 x 10 -8 b e t w e e n 1550 ~ to
1690~
D e r g e took 4 x 10 -9 as the a v e r a g e value of K ' .
T h e r e has been no d e t e r m i n a t i o n of the activity coeff i c i e n t of b o r o n in liquid i r o n or of the effect of boron
on the a c t i v i t y coefficient of oxygen in liquid iron.
It is the p u r p o s e of the p r e s e n t i n v e s t i g a t i o n to d e t e r m i n e the s o l u b i l i t y of oxygen and the a c t i v i t i e s in
F e - B - O and F e - V - O alloys. The activity of oxygen in
the a l l o y s was m e a s u r e d with the following g a l v a n i c
cells:

c a l c u l a t e d e o(V) to b e - 0 . 2 7 , - 0 . 1 1 , a n d - 0 . 2 9 , r e s p e c tively. F i s c h e r and H a u s s m a n n 4 d e t e r m i n e d e_(V)

o elec-

Cr-Cr2Os(s)[ ZrO2(CaO) I F e - V - O (l, s a t u r a t e d

with oxide)

[I]

t r o c h e m i c a l l y at 1600~ for a l l o y s c o n t a i n i n g up to 2.5

pct V and c a l c u l a t e d it to be - 0 . 1 3 . T h e r e has b e e n no
r e p o r t e d d e t e r m i n a t i o n of the activity of v a n a d i u m in
liquid F e - V alloys except the e s t i m a t i o n by D a s t u r and
C h i p m a n of the activity coefficient at infinite dilution

Cr-Cr~O3(s) [ ThO2(Y~O3) I F e - V - O (l, s a t u r a t e d

with oxide)

[H]

D e s p i t e the c o n s i d e r a b l e attention given in r e c e n t

y e a r s to the use of b o r o n in complex d e o x i d i z e r s , i n f o r m a t i o n on the t h e r m o d y n a m i c p r o p e r t i e s of F e - B - O
a l l o y s is e x t r e m e l y l i m i t e d . The only e x p e r i m e n t a l
work r e p o r t e d on the F e - B - O s y s t e m is that by D e r g e s
who m e a s u r e d the b o r o n , s i l i c o n , and oxygen c o n t e n t s
of liquid i r o n in e q u i l i b r i u m with s i l i c o b o r a t e m e l t s in
s i l i c a c r u c i b l e s . The slag c o m p o s i t i o n r a n g e d f r o m : 9
to 42 pct SIO2, 0.3 to 61 pct B2Os, and 11 to 71 pct FeO.
The deoxidation p r o d u c t K ' ,
g ' = (wt %B)2(wt ~oO) s
R. J. FRUEHAN is with E. C. Bain Laboratory for Fundamental
Research, U.S. Steel Corp., Research Center, Monroeville,Pa.
Mansucript submitted February 23, 1970.
METALLURGICALTRANSACTIONS

[2]

C r - C r g ) s ( s ) [ ZrO2(CaO) [ F e - B - O (l, BzO3, s a t u - [III]

r a t e d with Al~)3)
The r e l a t i o n s h i p between the m e a s u r e d e l e c t r o m o t i v e
f o r c e (E in mv) and activity of oxygen (ao) has been der i v e d p r e v i o u s l y 6 and is given by
log ao = 4.62 - 13~580 - 10.03 E
T

[3]

The r e f e r e n c e state for oxygen a c t i v i t y is at infinite

dilution in p u r e i r o n and the s t a n d a r d state 1 wt pct.
The a c t i v i t y of v a n a d i u m (a V) can a l s o be d e r i v e d
f r o m the m e a s u r e d e l e c t r o m o t i v e f o r c e , if the m e l t is
s a t u r a t e d with a v a n a d i u m oxide of known activity. D a s t u r and C h i p m a n I identified the oxide phase in e q u i l i b r i u m with F e - V - O to be Fe V204 for m e l t s c o n t a i n i n g
about 0.1 wt pct V, and V203 for the c o n c e n t r a t i o n s
g r e a t e r than 0.3 wt pct. A c c o r d i n g to the r e p o r t e d data
for the e n e r g i e s of f o r m a t i o n of v a n a d i u m oxides, 7'8 the
VOLUME 1,AUGUST 1970-2083

s t a b l e oxide p h as e would be VzO3 up to a v a n a d i u m a c t i v i t y of about 0.56 r e l a t i v e to p u r e solid v a n a d i u m . *

*Attempts to identifythe oxide phase m eqmhbnumwith a melt containing
26.2 wt pct V (av ~ 0.06) by X-raytechniqueswerenot entirelyconclusive.
However,there was strong evidencethat V203was the stableoxidephase.

At higher vanadium activities, VO would be the stable

oxide phase. In order to be assured that V203 was the
stable oxide phase, measurements
were restricted to
alloys with a vanadium activity less than about 0.I. The
overall cell reaction in the composition range investigated (0.3 to 36.3 pct V) can therefore be represented
by
_ V + ~ Cr203(s) = ~1 V203(s) * Cr(s)

[4]

The f r e e e n e r g y change a c c o m p a n y i n g R e a c t i o n [4] is

g i v e n by
AF = AF ~

2 . 3 0 3 R T log a v

[5]

and
~F

= - ne~

[6]

w h e r e n is the n u m b e r of e q u i v a l e n t s p e r m o l e , Eq. [3],

and 9 is the F a r a d a y constant. The a c t i v i t y of v a n a d i u m
is t h e r e f o r e given by
n~

log a V - 2.303 R T

(Eo-E)

[7]

w h e r e Eo is the e l e c t r o m o t i v e f o r c e of the c e l l f o r p u r e
s o l i d vanadium. The value of Eo ( - 2 1 7 m v at 1600~
w a s c a l c u l a t e d f r o m the known f r e e e n e r g i e s of f o r m a tion of Cr203 and V203. 7,s
The a c t i v i t y of b o r o n in F e - B a l l o y s can be e s t i m a t e d
in a s i m i l a r m a n n e r . The a c t i v i t y of boron a B is g i v en
by
ny
log aB _ 2.303
R T (EL-E)

+ ~- log aB203

[8]

w h e r e aB20~ is the a c t i v i t y of B203 and E~ is the e l e c t r o m o t i v e f o r c e of the c e l l f o r the B(s)-B203(l) s y s t e m . The value of E~ was c a l c u l a t e d f r o m the known
f r e e e n e r g i e s of f o r m a t i o n of B203 and CrzO37'8 and is
- 4 0 1 m v at 1550~
The e f f e c t of the t h i r d component, oxygen, on the a c t i v i t y of the second c o m p o n e n t in both the F e - V - O and
F e - B - O s y s t e m s can be n e g l e c t e d since its c o n c e n t r a tion is r e l a t i v e l y s m a l l . The h i g h e s t oxygen c on t en t inv e s t i g a t e d in the F e - V - O s y s t e m was about 0.4 wt p ct
and that in the F e - B - O w a s about 0.06 wt pct.
In o r d e r f o r Eqs. [3], [7], and [8] to be valid, the e l e c t r o l y t e s m u s t exhibit i n s i g n i f i c a n t e l e c t r o n i c c o n d u c tivity. It has been d e m o n s t r a t e d that ZrO~(CaO) e x hibits i n s i g n i f i c a n t e l e c t r o n i c conductivity down to about
5 x 10 -'3 atm 8 of oxygen at 1600~ and ThO2(Y203) down
to at l e a s t 2 10 -16 atm. 9 The e l e c t r o l y t e s w e r e not
u s e d below t h e i r r e s p e c t i v e oxygen p a r t i a l p r e s s u r e
l i m i t s in the p r e s e n t study.

EXPERIMENTAL
The g a l v a n i c c e l l s and the e x p e r i m e n t a l t e c h n i q u e
u s e d in the p r e s e n t study w e r e e s s e n t i a l l y the s a m e as
t ho s e d e s c r i b e d p r e v i o u s l y . ~'~~ The g a l v a n i c c e l l cons i s t e d of a ZrO2 (4 wt pct CaO) or a ThO2 (7 wt p ct
Y203) disk about 3 m m d i a m by 3 m m high s e a l e d into
2084-VOLUME 1,AUGUST 1970

one end of a s i l i c a tube. The tube was packed with a

powder m i x t u r e of C r - C r 2 0 3 which a c t e d as the r e f e r e n c e e l e c t r o d e . Contact with both e l e c t r o d e s w a s m a d e
with a m o l y b d e n u m w i r e . As d i s c u s s e d p r e v i o u s l y ,
m o l y b d e n u m c o n t a c t s a r e suitable in t h e s e e x p e r i m e n t s .
Initially 300 g of e l e c t r o l y t i c i r o n contained in a high
purity recrystallized alumina crucible was brought to
temperature
in a molybdenum-wound
resistance furnace which was continuously flushed with argon.
Pure vanadium (99.9 pct) or ferroboron (18.47 pct)
was added to the melt, and after waiting a sufficient
time to insure equilibrium, a galvanic cell was lowered
into the melt. The equilibrium oxide phase was formed
in the melt by the reaction of oxygen with the added
boron or vanadium.
The presence of an oxide was confirmed visually and when necessary additional oxygen
was added in the form of iron oxide. Stable reversible
readings ( 1.5 my) were obtained as in previous studies. 6'9'I~ In several Fe-V melts cells tipped with both
ZrO2(CaO) and ThO2(YzO3) were used, and they agreed
within 2 mv for alloys containing less than about 25 wt
pct V. Samples of the melt were taken and analyzed for
oxygen by the neutron activation technique for the Fe-V
alloys and by vacuum fusion technique for the Fe-B alloys.* The boron and vanadium contents were deter*The oxygencontent of alloyscontaininga significantamount of boron,
[wt(%B)/wt(%O)] > 1, cannot be determinedusing the neutron activationtechnique, becauseboron exhibitsa similarbehaviorto oxygenunder neutron activation.
m i n e d c h e m i c a l l y in the u s u a l m a n n e r .
P r e v i o u s i n v e s t i g a t o r s r e p o r t e d no s i g n i f i c a n t side
r e a c t i o n s when F e - V - O (saturated) m e l t s w e r e held in
a l u m i n a c r u c i b l e s . A l u m i n a is m u c h m o r e stable than
any of the o x i d e s of vanadium, and AleO3 and V203 do
not f o r m a liquid p h ase at 1600~ 1I A l u m i n a c r u c i b l e s
w e r e a l s o u s e d f o r the F e - B m e l t s b e c a u s e A1203 has
a l i m i t e d s o l u b i l i t y in B203. G i e l i s s e and F o s t e r I2 d e t e r m i n e d p a r t of the p h a s e d i a g r a m of the B20,-A1203
s y s t e m . The solubility of A1203 in liquid BzO3 at 1550 ~
and 1600~ in t e r m s of m o l e f r a c t i o n is 0.087 and 0.122,
r e s p e c t i v e l y . F o r this c o m p o s i t i o n r a n g e R a o u l t ' s law
may be a s s u m e d , giving 0.913 and 0.878 for the a c t i v i t y
of B203 in a l u m i n a - s a t u r a t e d m e l t s at 1550 ~ and 1600~
r e s p e c t i v e l y . T h e s e e s t i m a t e d v a l u e s of a B203 a r e u s e d
in Eq. [8] f o r e v a l u a t i n g the b o r o n a c t i v i t i e s f r o m the
m e a s u r e d emf.

R E S U L T S AND DISCUSSION
Fe-V-O
The s o l u b i l i t y of oxygen in F e - V m e l t s in e q u i l i b r i u m
with its oxide p h a s e s is p r e s e n t e d in Table I and plotted
in Fig. 1. The solubility r e a c h e s a m i n i m u m of about
180 ppm b e t w e e n 2.5 and 3.5 wt p ct V. The solubility
then i n c r e a s e s with i n c r e a s i n g v a n a d i u m content to
about 4000 ppm at 36.3 wt pct. The data of Chipman and
D a s t u r 1 a r e a l s o plotted f o r c o m p a r i s o n .
As d e m o n s t r a t e d in Fig. 2, the d eo x i d at i o n p r o d u c t
(%V)2(%O) 3 i n c r e a s e s m a r k e d l y with i n c r e a s i n g vanadium
content. Th i s, of c o u r s e , is p r i m a r i l y due to the e f f e c t
of v a n a d i u m on the activity c o e f f i c i e n t of oxygen in the
m el t .
The a c t i v i t y of oxygen was c a l c u l a t e d f r o m the m e a s u r e d e l e c t r o m o t i v e f o r c e s u s i n g Eq. [3]. T h e s e r e s u l t s
METALLURGICALTRANSACTIONS

Table 1. Solubility and Activity Coefficient

of Oxygen in Fe-V Alloys at 1600~

wt pct V

Nv

O, ppm

E, mv

log fo

av'}"

7vt

0.43
0.60
0.78
0.97
1 45
1.73
2.65
2.72

0.0047
0.0065
0.0085
0.0106
0.0158
0.0189
0.0287
0.0295
0.0389
0.0436
0.0445
0.0556
0.0665
0.155
0.163
0.223
0.259
0.280
0.377
0.0006
0.0008
0.0014

336
370
275
279
185
207
168
180
185
186
170
178
285
620
823
1260
1760
2063
4140
1210
634
596

199 (1)
181 (I)
163 (I)
147 (I)
125 (I)
114 (I)
94(I)
93(I)
76 (I)
68(1)
62 (I)
53 (I,II)
41 (I,II)
-18 (II)
-23 (II)
35 (II)
- 6 0 (II)
66 (II)
-100(II)
.
.
.
.
.
.

0.10
0.24
0.20
0.28
0.24
0.32
0.33
0.39
0.48
0.55
0.52
0.59
0.99
1.51
1.66
1.92
2.15
2.29
2.70
.
.
.

0.00044
0.00062
0.00085
0.00115
0.00174
0.00209
0.00316
0_00317
0.00436
0.00501
0.00562
0.00660
0.00831
0.0245
0.0276
0.0407
0.0537
0.0603
0.100
.
.
.

0.094
0 095
0.100
0.108
0.110
0.111
0.110
0.107
0.112
0.115
0.126
0 119
0 125
0.158
0.169
0.183
0.207
0.215
0.265

3.55
4.00
4 10
5.10
6.15
14.3
15.1
20.8
24.2
26.2
36.3
006*
0.07*
0.13"

0.17"

0.0018

458

--

are combined with the solubility data in calculating the

activity coefficient of oxygen (fo) in Fe-V alloys at
1600~ listed in Table I. The reference state is oxygen
at infinite dilution in pure liquid iron. The uncertainty
in log fo is estimated to be about 0.04. In Fig. 3 log
fo is plotted vs wt pct V indicating that the first-order
interaction coefficient e~V) is inadequate for describing
the results over the entire composition range. The use
second order interaction coefficient, '3 r~V) , does not
significantly improve the representation.
All of the preceding determinations
1-4 of eo(V) w e r e
c a r r i e d o u t f o r a l l o y s c o n t a i n i n g l e s s t h a n 3 w t p c t V.
In order to compare the present work with the previous
determinations,
a first-order
interaction coefficient
e~ V) w a s c a l c u l a t e d

E(V)

9 DASTUR 8 CHIPMAN
0 PRESENTWORK
-05 ",~,
x~.~--LIMITINGSLOPE-1/2

/
/

5000
2000

A
0

-J

iooo

-I0

500 6
-15

200
/

-2.0

MIXED /

FeV204""~ OXIDES~
I

-20

-I 0

I00

V203
I

1.0

Fig. 1 - - S o l u b i l i t y of o x y g e n in F e - V a l l o y s at 1600~

for the

( d In (yo/y~)~
:

dNv

[91

]NFe._, 1

where ~; is the oxygen activity coefficient in pure liquid

iron.
Using Eq. [7] the activity of vanadium at 1600~
relative to pure solid vanadium, is calculated from the
measured
e m I a n d i s g i v e n in T a b l e I. I n o r d e r t o c o m ply with Eq. [7], the activity calculations are limited to
alloys containing more than 0.47 at. pet and less than
3 7 . 7 a t . p e t V w h i c h a r e in e q u i l i b r i u m w i t h V203. T h e
values of log Yv are plotted vs N 2 in Fig. 4 in accordFe
ance with the quadratic formalism
p r o p o s e d b y D a r k e n . '4
The line of best fit through the data is represented
by

log ~ v

log (wt %V)

2.0

results

of Chipman and Dastur,' -0.27; Pargeter, 3 -0.29;

Schenck and Steinmetz, 2 -0.11; and Fischer and Haussmann,4 -0.13. These values are in fair agreement with
the present work considering the experimental scatter
and the limited composition range of the previous stud-

the present

ies. The value of e~V) determined in the present study

(-0.14) corresponds to Eo
V = --29, where

*No electromotwe force reading taken.

t RelaUve to solid vanadium.
( )Indicates cell used for measurement.

from

l i m i t i n g c a s e o f p c t V - - 0. T h e v a l u e o f e~ V) a t p c t
V ~ 0 is found to be -0.14 as compared with the values

= - 0.70

N~e-

0.30

giving an activity coefficient

= 0.10 and ~ FeV = -0.70.

'

'

[10]
o

at infinite dilution, Yv

'

'

1.0
0
-t.O

-I.0
o

-2.0
-3.0

-2.0
-40
-50
I

40
20
50
V,wt.%
Fig. 2 - - C o m p o s i t i o n d e p e n d e n c e of the d e o x i d a t i o n p r o d u c t
(wt % V)2(wt % O) 3 in F e - V - O m e l t s at 1600~
0

I0

METALLURGICAL TRANSACTIONS

-5.0

I0

20

50

40

V, wt.%

Fig. 3 - - A c t i v i t y c o e f f i c i e n t of o x y g e n in F e - V a l l o y s at
1600~
VOLUME 1,AUGUST 1 9 7 0 - 2 0 8 5

NFe
0.9
I

-0.50

0.8
I

0.7
I

06

0.5
I

-0.60

m i n e d in t h e p r e s e n t w o r k (1600~
However, the work
of M y l e s a n d A l d r e d i n d i c a t e s t h a t t h e a c t i v i t y of v a n a d i u m (1327~
approaches Raoult's law with increasing
v a n a d i u m c o n t e n t m o r e r a p i d l y t h a n f o u n d in t h e p r e s e n t
study.
Fe- B-O

-0.70

-0.80

- 0.90

- 1.00

0.80

0.60
2

0.40

-I.10

1.00

0.20

N Fe

Fig. 4--Activity coefficient of vanadium in Fe-V alloys at

1600~ (relative to solid vanadium).

D a r k e n 15 h a s a l s o d e f i n e d q u a d r a t i c f o r m a l i s m c o n stants for ternary alloys. The constant aVO defined by

E q . [11], w h i c h i s v a l i d a t i n f i n i t e d i l u t i o n , i s e q u a l t o
-11.9
E~V) = 2.303 ( ~ v o - ot FeO - ~ FeV)

[11]

T h e a c t i v i t i e s of v a n a d i u m a n d i r o n , c a l c u l a t e d f r o m
t h e G i b b s - D u h e m e q u a t i o n , a r e g i v e n in T a b l e II. T h e
a c t i v i t y of v a n a d i u m r e l a t i v e t o l i q u i d v a n a d i u m i s a l s o
p r e s e n t e d . In c h a n g i n g t h e s t a n d a r d s t a t e f o r v a n a d i u m
activity from pure solid to liquid, the melting point
(2190~
a n d e n t r o p y of f u s i o n (2.3 eu) c o m p i l e d b y H u l t g r e n e t a l . ~6 a r e u s e d .
T h e r e p o r t e d v a l u e s f o r t h e a c t i v i t y of v a n a d i u m i n
o
l i q u i d F e - V a l l o y s a r e l i m i t e d t o t h e e s t i m a t i o n of 7 V b y
o

C h i p m a n a n d D a s t u r . T h e y r e p o r t e d YV to b e 0 . 1 2 w h i c t
i s in g o o d a g r e e m e n t w i t h YV = 0 . 1 0 o b t a i n e d f r o m t h e
present work.
M y l e s a n d A l d r e d r7 d e t e r m i n e d t h e a c t i v i t i e s i n s o l i d
F e - V a l l o y s a t 1327~ u s i n g a t o r s i o n - e f f u s i o n t e c h nique. There does not exist sufficient thermodynamic
d a t a to m a k e a d i r e c t c o m p a r i s o n of t h e i r r e s u l t s w i t h
t h o s e d e t e r m i n e d in t h e p r e s e n t i n v e s t i g a t i o n . H o w ever, they did find negative deviations from Raoult's
law similar to the present work. For example, the act i v i t i e s of v a n a d i u m (1327~
d e t e r m i n e d by M y l e s a n d
A l d r e d a t N V = 0.1 a n d 0.2 w e r e 0 . 0 1 3 8 a n d 0 . 0 4 6 6 , r e s p e c t i v e l y , a s c o m p a r e d w i t h 0.014 a n d 0 . 0 3 6 d e t e r -

T h e e x p e r i m e n t a l r e s u l t s on t h e s o l u b i l i t y of o x y g e n
in l i q u i d F e - B a l l o y s in e q u i l i b r i u m w i t h A 1 2 0 3 - s a t u r a t e d l i q u i d B203 a r e g i v e n in T a b l e III a n d p l o t t e d in
F i g . 5. A t 1550~ t h e s o l u b i l i t y of o x y g e n d e c r e a s e s
w i t h i n c r e a s i n g b o r o n c o n t e n t t o a b o u t 80 p p m a t 0.2 w t
p c t B. T h e o x y g e n c o n t e n t r e m a i n s e s s e n t i a l l y u n changed with further increase in boron content up to
0 . 6 7 p c t B, w h i c h w a s t h e h i g h e s t b o r o n c o n t e n t i n v e s t i g a t e d in t h e p r e s e n t w o r k . T h e l e v e l i n g off of t h e o x y g e n s o l u b i l i t y c u r v e in F i g . 5 i s d u e t o t h e l o w e r i n g of
t h e a c t i v i t y c o e f f i c i e n t of o x y g e n w i t h i n c r e a s i n g b o r o n
c o n t e n t . In t h e l i m i t i n g c a s e of p c t B ~ O, t h e s l o p e of
the curve in Fig. 4 is equal to -~- as would be expected
f r o m t h e s t o i c h i o m e t r y of B203.
T h e a c t i v i t y c o e f f i c i e n t of o x y g e n in F e - B - O a l l o y s ,
r e l a t i v e t o o x y g e n in u n a l l o y e d i r o n , w a s c a l c u l a t e d
f r o m t h e s o l u b i l i t y d a t a a n d t h e a c t i v i t y of o x y g e n c a l culated from the measured electromotive force. The
c o m p o s i t i o n d e p e n d e n c e of l o g f o i s s h o w n i n F i g . 6;
within the experimental scatter the data obtained at
1600~ c o u l d n o t b e d i s t i n g u i s h e d f r o m t h a t a t 1550~
T h e v a l u e of t h e i n t e r a c t i o n c o e f f i c i e n t e~B)" a s p c t
B ~ O is -2.6.

The corresponding

v a l u e of E.(B) i s

- 115. T h e v a l u e of e~B) r e m a i n s r e l a t i v e l y c o n s t a n t up
to a b o u t 0.1 p c t B. H o w e v e r , a t h i g h e r b o r o n c o n t e n t s

Table III. The Solubility end Activity of Oxygen in Fe-B Alloys

Equilibrated with Molten B2OaSaturated with AI203

Boron, wt pct

Oxygen, wt pct

0.005
0.012
0.025
0.07
0.10
0.11
0.12
0.14
0.15
0.16
0.24
0.26
0.28
0.39
0.67

0.057
0.035
0.026
0.016
0.013
0.011
0.011
0.011
0.0080
0.0085
0.0081
0.0084
0.0079
0.0070
0.0080

E,* my

-log fo

278
229
200
137
105
105
80
77
74
72
42
40
28
17
-3

0.03
0.09
0.10
0.25
0.31
0.24
0.36
0.36
0.26
0.29
0.42
0.45
0.49
0.53
0.65

230
208
163
138
110
95
88
74

0.04
0.03
0.22
0.16
0.29
0.34
0.26
0.32

1550~

1600~
o

Table II. Activity of Iron and Vanadium in Fe-V Alloys at 1600 C

NV
0.00
0.10
0.20
0.30
0.40

av
0.014
0.036
0.069
0.108

7V

av

7V

aFe

(Sohd Reference) (Liquid Reference)

0.100
0.084
1.00
0.136
0.012
0.118
0.887
0.179
0.030
0.150
0.750
0.228
0.058
0.192
0.606
0.272
0.092
0.229
0.463

2086-VOLUME 1,AUGUST 1970

7Fe
1.00
0.986
0.938
0.865
0.772

0.01
0.03
0.05
0.08
0.11
O.12
0.17
0.23

0.045
0.033
0.029
0.019
0.018
0.017
0.013
0.012

*Cell III used for all measurements.

METALLURGICAL TRANSACTIONS

-1.0

|ooo

500
.I.5
2oo
3

LIMITINGSLOPE-

-2.0

IOO

50

-2.5
-2.5

-2.0

-l.5

-I.0

-0.5

lo(J (wt.% B)

Fig. 5--Solubility of oxygen in liquid F e - B alloys in equilibr i u m with B203 s a t u r a t e d with A120~.

0 1550~

-0.2

OC;

9 1600~ C

-0.4

-0.6

- 0.8
0

I
0.2

I
0.4

I
0.6

I
0.8

1.0

8, wt.%
Fig. 6--The activity coefficient of oxygen in liquid F e - B
alloys.

log fo is no l o n g e r a l i n e a r function of b o r o n content.

S i m i l a r b e h a v i o r was found for F e - V - O in the p r e s e n t
study and for the F e - C r - O 1~ s y s t e m p r e v i o u s l y r e ported.
F o r the deoxidation e q u i l i b r i u m
2 B ( 1 wt%) +3_O (1 wt%) =B~O3 (l, s a t u r a t e d
with Al~)3)

~-" -7.0
[13]

is 4.0 x 10-9 and 1.3 10-a at 1550~ and 1600~ r e spectively. If the activity of B203 adheres to Raoult's
law such that the activity of B203 in the alumina-saturated melt is 0.913 and 0.878 at 1550~ and 1600~ r e spectively, the values of the equilibrium constants for
pure B203 will be 4.4 10-9 and 1.5 I0 -s, respectively. Any error involved in the estimation of a B203
in the Al203-saturated melts is not too critical. If the
activity of B203 were as low as 0.6, the solubility of
oxygen in equilibrium with pure B203 would be about 13
pct lower than those calculated from the equilibrium
constant given above.
As mentioned previously, the only experimental deMETALLURGICAL TRANSACTIONS

-6.0

[12]

the e q u i l i b r i u m c o n s t a n t
g = (aB)2(ao) 3

t e r m i n a t i o n of the s o l u b i l i t y of oxygen in F e - B alloys

was that of Derge. 5 He e s t i m a t e d the deoxidation p r o d uct K ' = (wt % B)2(wt % O) 3 to be 4 10 -~. However, his
e s t i m a t i o n was an a v e r a g e value for v a r y i n g slag c o m p o s i t i o n s . The b e s t e s t i m a t e for the value of K ' which
can be d e t e r m i n e d from D e r g e ' s r e s u l t s is obtained by
plotting K ' vs wt pct B203 in the slag and e x t r a p o l a t i n g
it to 100 pct B203, where the a c t i v i t y of B203 is unity.
If this is done, the value of K ' obtained is about 3 x 10 -8
at the a v e r a g e t e m p e r a t u r e of about 1600~
It should
be s t r e s s e d that this is only a rough e s t i m a t e , since the
slag with the highest B203 content contained only 61 wt
pct B203, the t e m p e r a t u r e v a r i e d f r o m 1550 ~ to 1690~
and no a c c o u n t was taken for the effect of s i l i c o n or
b o r o n on the activity coefficient of oxygen. Despite
these l i m i t a t i o n s , this e s t i m a t e is in r e a s o n a b l e a g r e e m e n t with the p r e s e n t work.
In Fig. 7 log [(wt % B)2(wt % 0) 3] at 1550~ is p r e sented a s a function of c o m p o s i t i o n in o r d e r to d e m o n s t r a t e the effect of c o m p o s i t i o n on the s o l u b i l i t y p r o d uct. The s o l u b i l i t y p r o d u c t c h a n g e s m a r k e d l y with
c o m p o s i t i o n as was the case for F e - V - O s y s t e m shown
in Fig. 2. This is due to the effect of boron content on
the a c t i v i t y coefficients of oxygen and b o r o n in liquid
iron. The deoxidation e q u i l i b r i u m c o n s t a n t K is i n d e p e n d e n t of c o m p o s i t i o n , b e c a u s e due account is taken
for the change in the activity coefficients. The solubility p r o d u c t is only equal to the e q u i l i b r i u m deoxidation c o n s t a n t at infinite dilution of boron. Since K '
i n c r e a s e s with i n c r e a s i n g b o r o n content, it is not s u r p r i s i n g that D e r g e ' s a v e r a g e value for K ' is higher than
the value of the deoxidation e q u i l i b r i u m c o n s t a n t det e r m i n e d in the p r e s e n t work. It should be noted that
c u r v e s in F i g s . 2 and 7 can be r e p r e s e n t e d by s t r a i g h t
l i n e s only when the l o g a r i t h m of the activity coefficient
is a l i n e a r function of c o m p o s i t i o n . This is g e n e r a l l y
t r u e only in the dilute c o m p o s i t i o n r a n g e .
The c o m p o s i t i o n r a n g e of b o r o n was not l a r g e enough
in the p r e s e n t i n v e s t i g a t i o n to e v a l u a t e the d e p e n d e n c e
of the a c t i v i t y coefficient of b o r o n on composition. Howe v e r , f r o m the r e s u l t s an e s t i m a t e of the activity c o e i o
f i c i e n t at infinite dilution, ~B' ( r e l a t i v e to solid boron)

yoO

-8.0
.-4

-9.0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

wt.% B
Fig. 7--Composition dependence of the deoxidation product
(wt % B)~(wt % 0) 3 in Fe-B-O melts at 1550~
VOLUME 1,AUGUST 1970-2087

c a n b e m a d e u s i n g E q . [8]. A g a i n , a s s u m i n g t h a t t h e
a c t i v i t y of B203 at A1203 s a t u r a t i o n a t 1550~ i s 0 . 9 1 3 ,
o
t h e a v e r a g e v a l u e of YB i s 0.083. T h e a s s u m p t i o n t h a t
t h e a c t i v i t y of B203 o b e y s R a o u l t ' s law i n t r o d u c e s l i t t l e
o
e r r o r in the e s t i m a t e of YB" If t h e a c t i v i t y of B203 w e r e
o

u n i t y , TB w o u l d be 0.08; o r if t h e a c t i v i t y w e r e a s l o w
o

a s 0.6, YB w o u l d be 0.10.
CONCLUSIONS
T h e s o l u b i l i t y of o x y g e n in F e - V a l l o y s i s a m i n i m u m
of 180 p p m at 3 wt p c t V a n d i n c r e a s e s t o 4000 p p m at
36 w t p c t V at 1600~
T h e v a l u e of t h e i n t e r a c t i o n c o e f f i c i e n t , e~V) a s wt p c t V - - O i s - 0 . 1 4 (e~V) = - 2 9
a vo = -11.9).

as strong a deoxidizer as silicon. Boron decreases

= - 2 . 6 (e~B) = - 1 1 5 ) a t i n f i n i t e d i l u t i o n . T h e a c t i v i t y
c o e f f i c i e n t of b o r o n in l i q u i d i r o n a t i n f i n i t e d i l u t i o n i s
a b o u t 0.083 r e l a t i v e to p u r e s o l i d b o r o n . T h e d e o x i d a t i o n p r o d u c t s (%V)2(%O) 3 and (%B)2(%O) 3 a r e f o u n d to
i n c r e a s e m a r k e d l y w i t h i n c r e a s i n g c o n c e n t r a t i o n s of
vanadium and boron, r e s p e c t i v e l y . This s t r o n g c o m p o s i t i o n d e p e n d e n c e of t h e d e o x i d a t i o n p r o d u c t i s , of
c o u r s e , a m a n i f e s t a t i o n of t h e s t r o n g s o l u t e i n t e r a c t i o n s in t h e F e - V - O a n d F e - B - O l i q u i d a l l o y s .

and

The a c t i v i t y c o e f f i c i e n t of v a n a d i u m a d -

h e r e s to t h e q u a d r a t i c f o r m a l i s m w i t h c~ FeV = - 0 . 7 0
o

a n d l o g YV = - 1.0 ( r e l a t i v e to s o l i d v a n a d i u m ) .
B o r o n d e c r e a s e s t h e s o l u b i l i t y of o x y g e n in l i q u i d
i r o n d o w n to a b o u t 80 p p m a t 0.67 wt p c t B. It i s a b o u t

the

a c t i v i t y c o e f f i c i e n t of o x y g e n in l i q u i d i r o n w i t h eo(B)

ACKNOWLEDGMENTS
T h e a u t h o r w i s h e s to t h a n k L. J . M a r t o n i k f o r h i s a s s i s t a n c e in t h e e x p e r i m e n t s , E. T. T u r k d o g a n f o r h e l p ful d i s c u s s i o n s , G. W. M o m e y e r a n d h i s a s s o c i a t e s f o r
b o r o n a n d v a n a d i u m a n a l y s e s , a n d J. F. M a r t i n and h i s
associates for oxygen analyses.

REFERENCES
1. M. Dastur and J. Chipman AIME Trans, 1951, vol. 191, pp. 111-15.
2. H. Schenckand E. Stemmetz:Arch. Eisenhuettenw., 1967, vol. 38, pp. 871-74.
3. J. K. Pargeter: Can. Met. Quart., 1967, vol. 6, pp. 21-36.
4. W. A. Fischerand M. Haussmann:Arch. Eisenhuettenw, 1966, vol 36, pp.
959-61
5. G. Derge AIME Trans, 1946, vol. 167, pp. 93-107.
6. R. J Fruehan,L. J. Martomk, and E. T. Turkdogan: Trans. TMS-AIME, 1969,
vol. 245, pp. 1501-10.
7. J. F. Elhott, M. Glelser,and V. Ramaknshma: Thermochemistry for Steelmaking, Vol. 11,Addison-Wesley,1963.
8. Basic Open Hearth S teelmaking, AIME, 1964.

2088-VOLUME I,AUGUST 1970

9. R. J. Fruehan: Met Trans., 1970, vol. 1, pp. 865-70

10. R. J. Fruehan Trans. TMS-AIME, 1969, vol. 245, pp. 1215-18.
11. E. M. Levin,C. R. Robbins,and H. F. McMurdm'Phase Dtagramsfor Ceramists,
The AmericanCeramicSociety, 1964.
12. P. J. Glelisseand W. R. Foster Nature, 1962, vol. 195, pp. 69-70.
13. C. H. P. Lupis and J. F. Elhott ActaMet., 1966, vol 14, pp. 529-38.
14. L. S. Darken: Trans. TMS-AIME, 1967, vol 239, pp. 80-89
15. L. S. Darken Trans. TMS-A1ME, 1967, vol. 239, pp. 90-96.
16. R. Hultgren,R. Orr, P. Anderson,and K. Kelley"Selected Values of ThermodynamieProperties of Metals andAlloys, J. Wiley& Sons,New York, 1963.
17. K. Mylesand A. T. Aldred"J. Phys Chem., 1964, vol. 68, pp. 64-69.

METALLURGICAL TRANSACTIONS